Silver-organo-complex ink with high conductivity and inkjet stability

ABSTRACT

A robust formulation of silver-organo-complex (SOC) ink and method of making same are provided. In an aspect, the complexing molecules act as reducing agents. The silver loaded ink can be printed and sintered on a wide range of substrates with uniform surface morphology and excellent adhesion.

CROSS-REFERENCE TO RELATED DOCUMENTS

This application makes reference to, claims priority to, andincorporates by reference if fully set forth herein U.S. provisionalapplication No. 62/267,096 filed Dec. 14, 2015 titled“Silver-Organo-Complex Ink with High Conductivity and Inkjet Stability”.

TECHNICAL FIELD

The present disclosure generally relates to conductive inks for inkjetprinting.

BACKGROUND

Currently, a silver nanoparticle based inkjet ink is commerciallyavailable. This type of ink has several serious problems such as acomplex synthesis protocol, high cost, high sintering temperatures(˜200° C.), particle aggregation, nozzle clogging, poor shelf life, andjetting instability. For the emerging field of printed electronics,these short comings in conductive inks are barriers for their widespread use in practical applications.

SUMMARY

Provided herein are particle free conductive metal inks to address theaforementioned issues. In one or more aspects, particle free silver inksare provided that have high conductivity and inkjet stability. The inkscan be formulated of a silver-organo-complex (SOC). The inks can includecomplexing molecules that act as reducing agents.

In one or more embodiments, an SOC ink composition is disclosed. The inkcomposition can comprise a silver salt and a complex of a firstcomplexing agent and a second complexing agent and a carboxylic acid ora salt of a carboxylic acid. The silver salt can be selected from thegroup consisting of silver acetate, silver formate, silver carbonate,silver fluoride, silver nitrate, silver nitrite, silver chloride, silverbromide, silver iodide, silver phosphate, and silver oxide. The firstcomplexing agent can be an alkyl amine. The alkyl amine can be selectedfrom the group consisting of methylamine, ethylamine, propylamine,butylamine, and amylamine. The second complexing agent can be an aminoalcohol. The amino alcohol can be selected from the group consisting ofamino alcohols where in the alcohol is a C1-4 alcohol, such asmethanolamine, ethanolamine, propanolamine, or butanolamine. Thecarboxylic acid can be selected from the group consisting of carbonicacid, formic acid, acetic acid, propionic acid, butyric acid andpentanoic acid, and salts thereof. In one or more aspects, thecarboxylic acid can be a short chain carboxylic acid having a shortchain of 1-3 carbon atoms, and salts thereof. The short chain carboxylicacid can be carbonic acid, formic acid acetic acid and/or propionicacid. The ink composition can further include one or more additives foruse as an adhesive promotor. Suitable additives include 2%hydroxyethylcellulose (HEC), 2% 2-hydroxyethylcellulose and 2,3butanediol. A solvent can also be used to adjust the viscosity and/orsurface tension of the ink composition. The solvent can be, for example,water or an alcohol. The alcohol can be a low chain alcohol or asubstituted low chain alcohol. In one or more aspects, the low chainalcohol can have a short chain of 1-3 carbon atoms, i.e. methanol,ethanol, isopropanol, etc. The ink composition can have a pH of about 9to about 14 and any pH in between. For example, the ink composition canhave a pH of about 10.5. The ink composition can have a viscosity below9 mPA·s, for example about 4.95 mPA·s to about 5.97 mPa·s and anyviscosity in between. The ink composition can have a surface tension ofabout 30.7 mN/m to about 33.08 mN/m and any surface tension in between.The ink composition can have a sintering temperature of about 80 degreesCelsius to about 150 degrees Celsius and any temperature in between.

In one or more embodiments, a method of making the ink composition isprovided. The method can include the steps of combining theaforementioned silver salt and first and second complexing agents andcarboxylic acid or a salt of the carboxylic acid, to form an SOC inkcomposition of the present disclosure. The pH of the ink composition canbe adjusted to a desired value, such as within the range of 9 to 14.

In one or more embodiments, a method of forming a silver structure withthe aforementioned ink is provided. The method can comprise the steps ofloading an ink composition into a container, placing the container intoan ink deposition device (such as a printer with a nozzle and a means toload the ink into the nozzle), depositing the ink composition onto asurface, and reducing the ink composition that was deposited. The inkcomposition can be used for on-demand fabrication of the silverstructure. The silver structure can be a radio frequency (RF) electronicdevice. The RF electronic device can be an RF inductor, capacitor and/orfilter. The ink can be deposited with an about 1 pL piezoelectric nozzleof an ink deposition device to an about 10 pL piezoelectric nozzle of anink deposition device, and a nozzle of an ink deposition device candeposit a volume of about 1 pL to about 10 pL. The ink composition canbe deposited on a substrate, such as polyimide (PI), polyethyleneterephthalate (PET), polyethylene naphthalate (PEN), or glass.

Other systems, methods, features, and advantages of the presentdisclosure will be or become apparent to one with skill in the art uponexamination of the following drawings and detailed description. It isintended that all such additional systems, methods, features, andadvantages be included within this description, be within the scope ofthe present disclosure, and be protected by the accompanying claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Many aspects of the disclosure can be better understood with referenceto the following drawings. The components in the drawings are notnecessarily to scale, emphasis instead being placed upon clearlyillustrating the principles of the present disclosure. Moreover, in thedrawings, like reference numerals designate corresponding partsthroughout the several views.

FIG. 1A depicts an illustrative procedure for the formulation ofsilver-ethylamine-ethanolamine-formate-complex basedsilver-organic-complex (SOC) ink and the chemical reaction involved inthe formulation of ink.

FIG. 1B depicts a schematic presentation of a thermal reduction processfor printed ink conversion to silver metallic phase and chemicalreaction represented by ball-and-stick model.

FIG. 2A depicts thermogravimetric analysis (TGA) of the SOC ink.

FIG. 2B depicts differential scanning calorimetry (DSC) analysis of theSOC ink.

FIG. 2C depicts Fourier transform-infrared (FT-IR) spectrum for in situgas evolution during thermal decomposition.

FIG. 3A depicts ink-storage monitored by ultraviolet-visible (UV-Vis)spectrophotometer. The inset in FIG. 3A shows a photographic image of anSOC ink sample and a comparison with nanoparticle based ink (SilverjetDGP-40LT).

FIG. 3B depicts ink-jetting stability for a 10 pL cartridge monitored byevaluating average drop mass with number of days.

FIG. 3C number of working jets with delay time interval.

FIG. 4A depicts an inkjet-printed line pattern of SOC ink on glass and acorresponding scanning electron microscope (SEM) image.

FIG. 4B depicts the corresponding energy-dispersive X-ray spectroscopy(EDS) analysis of the line in FIG. 4A.

FIG. 4C depicts surface atomic force microscopy (AFM) topography forFIG. 4A.

FIG. 4D depicts 3D AFM topography for FIG. 4A.

FIG. 4E depicts an inkjet-printed line pattern of SOC ink on PEN and acorresponding SEM image.

FIG. 4F depicts the corresponding EDS analysis of the line in FIG. 4E.

FIG. 4G depicts surface AFM topography for FIG. 4E.

FIG. 4H depicts 3D AFM topography for FIG. 4E.

FIGS. 4I and 4J depict X-ray diffraction graphs for SOC based inksprinted on (I) glass and (J) PEN substrate, respectively. The sampleswere sintered at 150° C./30 min.

FIG. 5A depicts the resistance of 5×0.25 mm printed lines as a functionof printed layers.

FIG. 5B shows calculated conductivity as a function of overprints.

FIG. 5C depicts profiles of printed lines versus printed layers on aglass substrate.

FIG. 5D depicts an SEM image of a printed line on glass after beingsintered.

FIG. 5E depicts conductivity as a function of overprints on a 3D printedsubstrate.

FIGS. 6A-6H are cross-sectional SEM images of as-printed silver film onglass (FIGS. 6A-D) and PEN (FIGS. 6E-H) substrate with number ofprinting layers.

FIG. 7A depicts a microscope image of printed narrower lines with an ˜40μm gap.

FIG. 7B depicts a profile of the 40 μm gap in FIG. 7A.

FIG. 7C depicts a microscope image of printed narrower lines with an 18μm gap.

FIG. 7D depicts a profile of the 18 μm gap in FIG. 7C.

FIG. 8A is a conceptual depiction of an inductor with dimensionsdescribed herein.

FIG. 8B depicts a microscope image of a printed inductor.

FIG. 9A depicts inductance versus frequency for printed inductorssupported on a PEN substrate with a 1.5 turn inductance.

FIG. 9B depicts inductance versus frequency for printed inductorssupported on a PEN substrate with a 2.5 turn inductance.

FIG. 9C depicts quality factor versus frequency for printed inductorssupported on a PEN substrate with a 1.5 turn quality factor.

FIG. 9D depicts quality factor versus frequency for printed inductorssupported on a PEN substrate with a 2.5 turn quality factor.

FIGS. 10A-10D depict (A) Viscosity of VeroWhite™ dielectric ink (B) TGAof VeroWhite™ material after UV curing (C) dielectric constantproperties of VeroWhite™ material after UV curing (D) dissipationfactor. Bars represent the maximum and minimum measurement values offive test samples with the parallel plate method Agilent E4991 anddielectric test fixture 16453A.

FIGS. 11A and 11B depict (A) conductivity as a function of overprintinglayers at different sintering conditions, i.e., thermal heating at 150°C./30 min and IR heating at <80° C./5 min., and (B) SEM-focused ion beamcross-section of 8-layers of SOC ink with 5 minutes of IR<80° C.treatment after each overprint, respectively.

FIGS. 12 A-12D are cross section focused ion beam and SEM profiles of aprinted silver film of the present disclosure; and FIGS. 12E and 12H areSEM images of the corresponding surfaces.

FIG. 13 is a schematic presentation of the fabrication process for amultilayer inkjet-printed radio frequency electronics of the presentdisclosure.

FIG. 14 shows contact angle measurements showing the effect ofperfluorodecanethiol treatment on the spreading of the dielectric ink ontop of a solid printed silver layer at 5, 10 and 20 minutes, as comparedfor no treatment.

FIGS. 15A and 15B depict (A) white light interferometer of the 3Dprinted part with 1.8 μm in RMS roughness and (B) after a smoothinglayer of acrylic dielectric ink is applied with 0.4 μm in RMS roughness,respectively.

FIGS. 16 A and 16B show (A) capacitance at low frequency as a functionof temperature, and (B) quality factor, tested at 1 V AC signal and 0 Vbias condition. 11-μm-thick printed layers.

FIGS. 17A-17D show (A) a capacitor measured and simulated, (B) thequality factor of the capacitor (capacitor area is ˜0.9 mm² with an11-μm dielectric), (C) an Inductor measured and simulated and (D) thequality factor of the inductor (1.5 turn inductor with an outer radiusof 4 mm and 600-μm-thick lines), respectively.

FIGS. 18A-18D (A) microscope image of the printed filter, (B) SEMfocused ion beam cross-section image through the capacitor area, showingthe thickness of the printed dielectric and the top and bottomelectrodes of the filter, (D) measured and simulated S₂₁ filter responseversus frequency, and (D) zoomed in view of the filter response.

FIG. 19 shows Table 1. Ink-formulations A-F and ink properties withdifferent additives.

DETAILED DESCRIPTION

Described herein are various embodiments of the present systems andmethods for our SOC ink. Although particular embodiments are described,those embodiments are mere exemplary implementations of the system andmethod. One skilled in the art will recognize other embodiments arepossible. All such embodiments are intended to fall within the scope ofthis disclosure. Moreover, all references cited herein are intended tobe and are hereby incorporated by reference into this disclosure as iffully set forth herein. While the disclosure will now be described inreference to the above drawings, there is no intent to limit it to theembodiment or embodiments disclosed herein. On the contrary, the intentis to cover all alternatives, modifications and equivalents includedwithin the spirit and scope of the disclosure.

Discussion

Before the present disclosure is described in greater detail, it is tobe understood that this disclosure is not limited to particularembodiments described, as such may, of course, vary. It is also to beunderstood that the terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting, since the scope of the present disclosure will be limited onlyby the appended claims.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit (unlessthe context clearly dictates otherwise), between the upper and lowerlimit of that range, and any other stated or intervening value in thatstated range, is encompassed within the disclosure. The upper and lowerlimits of these smaller ranges may independently be included in thesmaller ranges and are also encompassed within the disclosure, subjectto any specifically excluded limit in the stated range. Where the statedrange includes one or both of the limits, ranges excluding either orboth of those included limits are also included in the disclosure.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present disclosure, the preferredmethods and materials are now described.

All publications and patents cited in this specification are hereinincorporated by reference as if each individual publication or patentwere specifically and individually indicated to be incorporated byreference and are incorporated herein by reference to disclose anddescribe the methods and/or materials in connection with which thepublications are cited. The citation of any publication is for itsdisclosure prior to the filing date and should not be construed as anadmission that the present disclosure is not entitled to antedate suchpublication by virtue of prior disclosure. Further, the dates ofpublication provided could be different from the actual publicationdates that may need to be independently confirmed.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentdisclosure. Any recited method can be carried out in the order of eventsrecited or in any other order that is logically possible.

Embodiments of the present disclosure will employ, unless otherwiseindicated, techniques of chemistry, synthetic inorganic chemistry,analytical chemistry, and the like, which are within the skill of theart. Such techniques are explained fully in the literature.

It is to be understood that, unless otherwise indicated, the presentdisclosure is not limited to particular materials, reagents, reactionmaterials, manufacturing processes, or the like, as such can vary. It isalso to be understood that the terminology used herein is for purposesof describing particular embodiments only, and is not intended to belimiting. It is also possible in the present disclosure that steps canbe executed in different sequence where this is logically possible.

It must be noted that, as used in the specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the context clearly dictates otherwise. Thus, for example,reference to “a support” includes a plurality of supports. In thisspecification and in the claims that follow, reference will be made to anumber of terms that shall be defined to have the following meaningsunless a contrary intention is apparent.

Disclosure

The field of printed electronics deals with several kinds of conductiveinks, including nanoparticles, nanowire, and two-dimensional sheets,which are based on metal, silicon, carbon, and oxide semiconductors.¹⁻⁷However, the printed electronics market is currently dominated byconductive metal nanoparticle based inks. The fabrication of highquality and low cost electronics requires innovative ink formulationsthat are cheaper and faster than traditional production methods. Atpresent, most of the conductive inks available are based on silvernanoparticles.⁸⁻¹²

As a requirement, ink must be stable to aggregation and precipitation toachieve reproducible performance. To meet this requirement silvernanoparticle ink normally uses organic stabilizers; unfortunately thestabilizers also can act as insulators.¹² Moreover, silver nanoparticleink with a high solid content can be more prone to stability issues,which can result in clogging of the inkjet nozzles and concerns aboutshelf-life of the ink.¹³ High silver loading can be beneficial, but thehigh temperature removal of organic stabilizers from the nanoparticlescan limit the choice of the substrate. Several sintering techniques(e.g. intense pulsed light, UV-curing¹⁴, microwave¹⁵, photonic¹⁶, andlaser curing¹⁷) have been reported to lower the sintering temperature,while remaining compatible with polymer substrates. Although thesemethods can be suitable alternatives, they have the disadvantage ofrequiring high temperatures for the thermal sintering. Fortunately,there is room for tuning the ink chemistry to reduce the temperature.⁸

Compared to nanoparticles, metal-organo complex based ink has recentlyreceived attention as a potentially lower cost alternative that can bestable at concentrations approaching saturation; neither additionalstabilizers nor reducing agents are required.¹⁸⁻¹⁹ Inkjet printing withthe use of particle free metal-organic-complexes or salts of variousmetals is a low-cost technology for direct metallization.²⁰ By adjustingthe viscosity and surface tension of the solution complex ink-chemistry,this type of ink could be used for various deposition techniques (e.g.,spin-coating, direct ink writing, fine nozzle printing, airbrushspraying, inkjet-printing, screen printing, and roll-to-roll processingmethods) in order to fabricate conductive tracks. A silver salt (20 wt %silver) solution in methanol/anisole (ink purchased from TEC-IJ-040,InkTec Co., Ltd, Korea) was utilized by Perelaer et al.²¹ Their studydemonstrated that printed silver tracks on glass have a conductivity of1.2-2.1×10⁷ S/m at 150° C.

Reactive silver inks, including ammonium hydroxide as a complexing agentand formic acid as a reducing agent, have been reported by Walker etal.²² Such a reactive ink decomposes too quickly, however, even at roomtemperature. Thus, it may not be suitable for long-term inkjet printingprocesses because it may lead to the formation of silver particles inthe nozzle and clog it. In addition, fast vaporization of ammonia andcarbon dioxide during the heating process can lead to gas bubbles. Thesegas bubbles from the vaporization of the silver ink components coulddrastically decrease the quality of the silver film and interfere withadhesion of the silver to the substrate. Despite these possibledrawbacks, this ink possessed a conductivity at 90° C., which is almostequivalent to that of bulk silver.

A similar ink has been tested by Liu et al.²³ using laser directpatterning of silver film on polymer substrate. Chen et al.²⁴spin-coated Ag(dien)](tmhd)/hexylamine/ethyl cellulose based ink on a PIsubstrate, and then annealed it at 250° C. for three hours; theyobtained a conductivity of 1-2.1×10⁷ S/m depending on film thickness.Recently, Dong et al.²⁵ synthesized MOC ink through a two-step process.First, silver oxalate was synthesized by silver nitrate and thendissolved in ethylamine as a complexing ligand, with ethyl alcohol andethylene glycol as a solvent, using a low temperature (0° C.) mixingprocess. The printed patterns on the PI substrate that were cured at150° C. for 30 minutes showed metalized silver with a conductivity of1.1×10⁷ S/m.

The methods described above for formulating silver complex based inksuffer from several drawbacks. In some cases a multi-component solventin the ink can have negative effects, and the ink can be less stablewith poor electrical properties and film formation even athigh-temperature annealing. In most of the reported SOC inks, adhesionwith the substrate is either not provided or discussed and jettingstability is not examined. For commercial utility, the design of silvercomplexation should meet the various requirements such as in situreduction, optimal viscosity, storage & jetting stability, smoothuniform sintered films, and high conductivity. In the field of printedelectronics, like other emerging electronic technologies, new materialsand processing methods are required for their ever-improving developmentand performance.

Disclosed herein is a novel SOC ink to address the aforementioneddisadvantages and shortcomings of previous inks. In any one or moreaspects, an ink composition for making a silver structure is provided.The ink composition can comprise: a silver salt; an organo-complex of afirst complexing agent and a second complexing agent; and a carboxylicacid or a salt of the carboxylic acid. The first complexing agent can bean alkyl amine. The alkyl amine can be selected from the groupconsisting of methylamine, ethylamine, propylamine, butylamine, oramylamine. The second complexing agent can be an aminoalcohol. Theaminoalcohol can be selected from the group consisting of methanolamine,ethanolamine, propanolamine, or butanolamine. The carboxylic acid can becarbonic acid, formic acid, acetic acid, propionic acid, butyric acid,pentanoic acid, a salt thereof, or any combination thereof. In one ormore aspects, the carboxylic acid can be a short chain carboxylic acid,i.e. having 1-3 carbon atoms, such as carbonic acid, formic acid, aceticacid, propionic acid, a salt thereof, and any combination thereof.

In any one or more aspects, the ink composition can include a solventand/or a stabilizer. The solvent can be water an alcohol, and acombination thereof. The alcohol can be a short chain alcohol having analkyl chain of 1-3 carbon atoms. The ink composition can have has a pHof 9-14, for example an adjusted pH of about 10.5. The ink compositionink can include an additive to promote adhesion. The additive can beselected from the group consisting of HEC, 2-HEC, 2,3-butanediol,glycerol, or ethylene glycol. As an example, the additive can be about2% 2-HEC. The ink composition can have a viscosity of less than 9 mPa·s,for example about 4.95 mPa·s to about 5.97 mPa·s. The ink compositioncan have a surface tension of about 30.7 mN/m to about 33.08 mN/m. Theink composition can have a sintering temperature of about 80 degreesCelsius to about 150 degrees Celsius. In an aspect, the present ink canbe a silver-ethylamine-ethanolamine-formate-complex based transparentand stable ink. The ethylamine, ethanolamine, and formate species canact as in situ complexing solvents and reducing agents. Theas-formulated ink composition can be inkjet printed on a wide range ofsubstrates, including (but not limited to) PI, PET, PEN, glass, andother 3D-printed substrates, such as those formed from acrylic and/ormolten plastic (acrylonitrile butadiene styrene (ABS), polylactic acid(PLA), etc) based materials. By adjusting the viscosity and surfacetension of the ink composition, the ink can be used for various inkdeposition techniques, including spin coating, direct ink writing, finenozzle printing, airbrush spraying, screen printing and roll-to-rollprocessing methods.

Decomposition of the ink (i.e., the process of solvent evaporation withheat after the ink is jetted from a nozzle onto a target substratesurface) in the present disclosure can lead to uniform surfacemorphology with excellent adhesion to the substrates. The jetting andstorage stability can be monitored, and the inks can be highly stablewith jetting for repeated performance. The ink can have highconductivity. Combining these characteristics with the high conductivityof the ink, fabricated RF electronic devices can be printed which candemonstrate suitable performance. For example, Inductor values can berealized up to 35 nH with quality factors greater than 10 at frequenciesabove 1.5 GHz and can prove the viability of the ink as a suitablematerial for the fabrication of printed electronics.

EXAMPLES

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how toperform the methods and use the compositions and compounds disclosed andclaimed herein. Efforts have been made to ensure accuracy with respectto numbers (e.g., amounts, temperature, etc.), but some errors anddeviations should be accounted for. Unless indicated otherwise, partsare parts by weight, temperature is in ° C., and pressure is in bar.Standard temperature and pressure are defined as 0° C. and 1 bar.

Example 1

Ink Chemistry

The as-formulated ink can be free of particles and can be stable in asealed glass vial at room temperature. Storage stability can beextended, however, if the ink is stored in an opaque vial andrefrigerated at 4° C. The ink can be prepared through the complexationbetween the silver salt, in this example silver acetate, pH controlledcomplexing solutions, and a short chain carboxylic acid which in thisexample is formic acid. The complexing solutions in this examplecontained ethylamines and ethanolamines as the first and secondcomplexing agents, acetate anions from the silver acetate in solution,and formate anions from the formic acid.

The lone pairs of electrons on the nitrogen atoms of ethylamine andethanolamine can coordinate with silver cations from the silver salt andthey may form Ag(ethylamine-ethanolamine) complexes that can be balancedwith the formate anions (FIG. 1A). Usually, silver-amines complexes canhave very high solution pH (for example, pH=14 or higher) and could notbe used for effective ink reduction and decomposition, but with theaddition of formic acid and adjustment of solution pH below 14, in thisexample to 10.5, the resultant ink can have suitable stability anddecomposition at elevated temperature. An ink composition with a of pH10.5 can provide suitable chemical stability. However, further reductionof the solution pH (for example, below 9) may lead to instability andlower silver loading. Thus, in some instances both amine combinationsmay be necessary not only for chemical stability but also for itsdecomposition at lower temperature with high conductivity. As the ink isheated above 80° C., elemental silver can be the only phase thatremains. Pure elemental silver can result from the decomposition andreduction of complexes by the formate anion, which can lead to the slowevaporation of ammonia and carbon oxide along with the low boiling pointreactants (FIG. 1B).

To assess the quality of the ink, jetting stability and final filmquality can be investigated. The ink composition can be formulated insuch a way that the constituent solvent not only acts as a complexingand reducing agent, but it also can provide a more optimal viscosity andsurface tension for ink jetting performance. Initially, theas-formulated ink can have a viscosity of ˜4.95×10⁻³ Pa·s and a surfacetension of 33.08 mN/m, which can be adequate for jetting. With theaddition of 2-hydroxyethylcellulose (2-HEC), the ink can demonstrateenhanced viscosity of ˜5.97×10⁻³ Pa·s and reduced surface tension of30.7 mN/m, which can provide good jetting and can improve adhesion. Anink with a viscosity of ˜9.0×10⁻³ Pa·s did not jet successively. Thus,in this particular set-up an ink having a viscosity less than ˜9.0×10⁻³Pa·s is preferred.

Several additives were investigated that can promote adhesion, such as2% hydroxyethylcellulose (HEC), 2% 2-HEC, 2,3-butanediol, glycerol,ethylene glycol. It is observed that even without any additive, the inkcan possess good adhesion on substrates and can have good jetting andstorage stability. With the addition of an adhesive promotor likecellulose (i.e. 2-HEC or HEC), the ink can show excellent adhesion ascompared to glycol-based additive or no additive. See Table 1 (FIG. 19).

It is well documented that cellulose based molecules can possessself-adhesion. Several theories have been proposed to provide anexplanation for the adhesion phenomenon such as: adsorption,electrostatic attraction, and diffusion; however, there is currently nosingle theory that can explain adhesion in general, as has beendiscussed in literature.²⁶ Further discussion on nanoparticle basedfilm's adhesion to substrates through adhesion promotors can be found inreferences below.^(27,28)

As can be seen, the adhesion enhancement phenomenon due to promotors isa complex issue and can be explained based on multiple theories. In thepresent case, an explanation can be that the ink with promotor(additive) shows good wettability on the substrate, and it could bepresumed that the physical adsorption due to van der Waals attractionforce and acid-base interactions is contributing to the adhesion forces.It was realized that water compatible (HEC) can be a choice for thepresent ink-formulation even with 2% wt, and can provide sufficientviscosity. All of the ink can be jetted successfully, except for inkwith 2% HEC. It is observed that even at high voltage with an efficientwaveform the fluid can be driven out of the orifice but then can recoilback inside. 2-HEC (MW-90000) also can exhibit excellent jettingbehavior.

Thermal Analysis of Ink

The thermal decomposition of the ink and the Fourier transform-infrared(FT-IR) spectra of gas evolution during the process can be determinedusing a thermogravimetric analysis infrared (TGA-IR). TGA and DSCanalysis can be performed on the SOC ink. FIGS. 2A, 2B and 2C show theTGA and Gram-Schmidt curves, differential scanning calorimetry (DSC)curve, and FT-IR spectrum scans (for in situ gas evolution duringthermal decomposition) of the SOC ink, respectively.

Storage and Jetting Stability of Ink

Particle free ink can be formulated which may not aggregate or clogduring printing. The ink can provide both jetting stability and longterm storage. The ink storage stability can be monitored using a UV-Visspectrophotometer. Absorption spectra from SOC ink one month afterstorage, filtered SOC ink, and Silver nanoparticle (NP) reference inkare shown in FIG. 3A. The absorption spectra from inks are featureless.Moreover, the absorption spectra shows weak absorption in the 400-425 nmrange, where absorption is typically associated with the presence ofsilver particles (0.1% DGP-40LT silver NPs ink). This finding confirmsthat the ink was particle-free. After one month of storage, there was nosign of silver formation in the UV spectrum and the ink remainedtransparent. Rheological measurement of the ink was also examined forfreshly prepared ink and after two to three weeks of storagecorroborated a lack of silver particle formation.

The graphs show that there is no substantial change in viscosity withstorage time (2 to 3 week) when applying shear rate of 0.1-1200 1/s. Toprovide further insight with storage and jetting stability, theevaporation rate of the ink can be investigated by thermogravimetricanalysis. The ink can be kept at different isothermal temperatures i.e.28, 80 and 150° C. for a period of time of two hours in constant airflow (20 mL/min) environment. However, it is worth mentioning here thatthese test conditions may not be a true representation of the ink in thecartridge, where ink may not be very exposed and may not have anoperating cartridge temperature of more than 60° C. As expected, theevaporation rate of the solvents at 28° C. can be much slower than thesolvent evaporation rate at 80° C. and 150° C. More than 50% of the inkconstituent can retain over the period of 6 h at 28° C. However, whenthe isothermal temperature is increased to about 80° C. and about 150°C., ink solvents can evaporate completely with faster rates (150° C.within about 30 min and 80° C. in about 2 h). It could be assumed thatcomplete evaporation at 80° C. needs more time than usual.

Apart from ink storage stability, it can be important to investigate theink's jetting stability with time using a conventional 10 pL nozzle aswell as with a 1 pL nozzle. Evaporation of the ink in the nozzle canlead to clogging of the head as well as a decrease in drop mass overtime. There are several reports²²⁻²⁵ where authors have presentedparticle free ink-formulations, but none report jetting stability overtime. If the ink is very reactive, such as silver-amino complex basedreactive ink that can decompose even at room-temperature, then there isa chance of the ink drying in the nozzle.²²

However, in our ink formulation low and high boiling amines not onlycomplex with silver, they can act as a co-solvent to suppress theevaporation rate. Methanol can be added to adjust the surface tension(30.7±0.5) of the ink, which is almost stable over a time, and thus canstabilize the ink performance. Ink storage can be monitored byultraviolet-visible (UV-vis) spectrophotometry for a 10 pL cartridge canbe monitored, as demonstrated in FIG. 3A. Ink-jetting stability can alsobe measured, and FIG. 3B shows a graph of the average drop massmonitored over 5 months for 10 pL nozzles, which can be fairlyconsistent at just under 7 ng. The nozzles with 1 pL also showconsistent average drop mass of less than 1.25 ng over 3 week time. Theink can be kept in a refrigerator at 4° C. for storage. The inset inFIG. 3A shows a photographic image of an ink sample and its comparisonwith nanoparticle based ink (Silverjet DGP-40LT). Jetting stabilitytests can confirm that the ink can be highly stable with jetting forrepeated performance.

The effect that delay time interval has on the number of working jetswas also investigated, as presented in FIG. 3C. The number of workingnozzles means that when the delay test starts, there can be 16 totalnozzles available to jettison the ink, with a print volume per each ofthe 16 nozzles in the range of 1 pL to 10 pL (in, for example, apiezoelectric based inkjet printer, such as a Dimatix DMP-2831 printer),which drop the ink continuously. With every delay time interval, nozzlesare paused and re-played and the working ability of the nozzles isassessed. Up to 30 minutes of delay, almost all the nozzles worked well.As the delay time interval increases from 30 to 60 mins, the number ofworking nozzles dropped from 16 to a total of 9, which further droppedto 1 after a 90 min delay. Most of the nozzles stop working after a 90min delay and the likely reason is the evaporation of ink in the nozzle.However, after 0.1 s purge, all 16 nozzles can again restart and followthe same delay trends. This may not be an issue in an industrialprinting environment, because after a short purge (0.1 seconds), alljets can return to the initial working state. Interestingly, a delaytest with 1 pL nozzles can show much better performance than 10 pLnozzles. With 1 pL nozzles and up to 180 minutes of delay, only 2nozzles stopped working and rest of the nozzles can work perfectly. Thereason is obvious as due to less opening of nozzle compared to 10 pLnozzles (9 μm), evaporation of ink can be much restricted in the nozzle.

Morphological & Electrical Evolution of Printed Silver Film as aFunction of Thermal Sintering

FIGS. 4A-4H show scanning electron microscopy (SEM), energy-dispersiveX-ray spectroscopy (EDS) analysis, and atomic force microscopy (AFM)images of SOC ink printed on glass (FIGS. 4A-4D) and PEN (t=125 μm,FIGS. 4E-4H) substrate. The images show that as-sintered particles caninterconnect with each other and satisfy a three-dimensionallyinterconnected conduction pathway via inter-particle neck growth with asintering temperature of 150° C./30 min. The printed silver line on theglass can have a line width of ˜54 μm (FIG. 4A). The EDS spectrumdemonstrated that the as-sintered films can be made of silver onlywithout any impurities (FIG. 4B). AFM topography of the printed filmshows that as-sintered films can be densified without any structuraldefects, and can have a root-mean-square (RMS) roughness of ˜94.7 nm(FIGS. 4C & 4D). In contrast to printing on glass, the silver line widthof ˜53 μm on PEN can have less connected smaller particles with silveras an elemental phase (FIGS. 4E and 4F) and with a roughness of ˜44.5 nm(FIGS. 4G-4H). FIGS. 4I and 4J show X-ray diffraction graphs of theprinted films on glass and PEN substrates, respectively. The observeddiffraction peaks are well matched and indexed to face-centered cubicsilver (JCPDS NO. 04-0783).³² The strong and sharp peaks indicate thatthe silver films can be highly crystalline and sintered.

To evaluate the electrical performance of SOC ink on glass and PENsubstrate, 5×0.25 mm electrode lines can be printed as a function of theover-printing number. Sintering can be performed at 150° C. for 30minutes after printing each layer. FIGS. 5A and 5B show graphsillustrating 4-point DC probe measured resistance (FIG. 5A) andcalculated electrical conductivity (FIG. 5B) as a function of the numberof over-printing layers on both glass and PEN substrates. FIGS. 5C and5D show width scan profile graphs and an SEM image of the printed lines.The thickness of printed electrodes can increase in a fairly linearmanner with the number of printed layers. Initially, single printingdemonstrated conductivities of ˜0.66×10⁷ and ˜0.4×10⁷ S/m on glass andPEN can be obtained respectively. Differences in conductivity ondifferent substrates are frequently observed.^(33,34) FIG. 5E shows agraph illustrating 4-point DC probe measured electrical conductivity asa function of the number of over-printing layers on 3D printed substrate(Vero Ink, Stratasys Objet printer). The 3D printed substrate can bechosen because of its low glass transition temperature (˜50° C.). TheAOC ink can provide a suitable 1×10⁷ S/m, (20%) of bulk conductivity atonly 80° C. using a low cost IR lamp. It is interesting to note that,usually, nanoparticle-based silver ink may not show any conductivity atthis processing temperature.

To investigate the conductivity difference on glass (FIGS. 6A-6D) andPEN (FIGS. 6E-6H) substrates, cross-sectional SEM images were checkedand it can be observed that the first layer of the printed film on PENsubstrate has not been sintered well, as nano-particles in theunderlying layer can be clearly seen (marked with an arrow in FIGS.6E-6H). This may be attributed to the lower thermal conductivity of PENas compared to the glass substrate. However, with the amount ofover-printing the conductivities of the printed structure cansubstantially be increased. With single printing and sintering, due tothe presence of voids between the films, percolated conductive pathwaysmay be limited. Because the ink can be particle free and can have aliquid-like behavior, when it was over-printed on sintered film it cango deep into the film and fill the voids after sintering and enhancethree-dimensional interconnection. Cross-sectional SEM images ofover-printed lines on glass and PEN substrates can show that the voidsin the film may be filled (see, FIGS. 6A-6H).

With printing numbers of seven to eight, the conductivity can saturateat ˜2.43×10⁷ and ˜2.12×10⁷ S/m on glass and PEN, respectively. Thepreviously reported reactive silver ink²² can have higher conductivityas highlighted in Supporting information, Table 2. Table 2 compares theperformance properties of several other SOC and nanoparticle inks andconsidering all requirements on jetting stability, adhesion, andstorage, this SOC ink can distinguishes itself from other works.

TABLE 2 A comparison of conductivities obtained using various silverinks Sintering Conductivity *Silver Method *Jetting Temperature (S/m)Ink Adhesion of Stability (° C.)/Time ×10⁷/Film Type Test depositiontest (in minute) thickness Substrate Ref. Silver — Inkjet NP Argon-     0.35/NP PEN 16 NPs Printing plasma/ 20 min Silver — Inkjet NP 150/5min 1.2-2.1/0.875 μm Glass 21 salt Printing solution in methanol/anisole (TEC-IJ- 040) Silver — DirectInk NP 90/15 min almost bulk/NPGlass 22 acetate/ writing ammonium hydroxide/ formic acid/ 2,3 butandiol[Ag(dien)]/ — Spin- NP 250/180 min 1-2.1/0.106 μm PI 24 (tmhd)/ costinghexylamine/ ethyl cellulose Silver Good Inkjet NP 150/30 min 1.1/1.2 μmPI 25 oxalate/ Printing ethylamine/ ethyl alcohol/ ethylene glycolSilver- Excellent, Inkjet Excellent 150/30 min 2.12/3.89 μm PEN Thisethylamine- 5B Printing work ethanolamine- formate- complex Silver-Excellent, Inkjet Excellent 150/30 min 2.43/4.25 μm Glass Thisethylamine- 5B Printing work ethanolamine- formate- complex NP = notprovided.

Adhesion Test of Printed Silver Film to Hard & Soft Substrates

The adhesion of the printed ink to several substrates, including glass,polyimide (PI), and PET films, can be assessed. Scotch® tape can be usedto test adhesion by applying tape to the entire region of the eachsilver film. After removing the tape, the samples were inspectedvisually to determine the amount of silver that was removed from thesubstrate. It can be observed that the ink can possess suitableadherence to all of the substrates without any post-resistance change.All plastic films can also be stressed and bent with no observeddecrease in adhesion of the silver film or any change in resistance.

Inkjet-Printing Smaller Features

Due to the particle free nature of this SOC ink and the excellentperformance through a conventional inkjet nozzle (10 pL) presented inthe previous sections, a smaller nozzle (1 pL) can be used without anyclogging or flow issues. The spreading and drying of SOC ink may not beinhibited by particles and may need to be carefully controlled to obtainfine features. The minimum printed feature sizes and gaps can beinvestigated, which are of interest in electronics design. For printingnarrow line traces, substrate surface energy should be uniformthroughout the substrate area. To create uniform surfaces, glasssubstrate can be spin-coated (5000 rpm for 40 s) with a layer of PVPhaving a thickness of ˜100 nm (5 wt % in 1-hexanol with 0.77 wt % ofcrosslinking agent poly (melamine-co-formaldehyde) and heated at 180° C.for 10 minutes prior to printing. FIGS. 7A-D show microscopic images andprofiles of printed line tracks using a 1 pL nozzle sintered at 150° C.for 30 minutes and 20 μm drop-spacing, which can result in minimum linespacing of ˜40 μm (image FIG. 7A & profile FIG. 7B) and ˜18 μm (imageFIG. 7C & profile FIG. 7D) with a line width of ˜20 μm. These aresuitable results for any inkjet-printed electronic applications whichrequire small feature sizes.

Inkjet-Printed RF Inductors

There have been several reports of RF inductors³⁵⁻³⁸, however due to thesensitivity to metal conductivity, thickness, and roughness, highquality inkjet-printed RF inductors remain elusive. RF inductors are afundamental building block in circuits. Planar spiral inductors arecommon and Intel corp. has demonstrated inductors with quality factors(Q's) greater than 20, utilizing 8 μm of highly conductive metal.³⁹Surface mount wire wound inductors are more complex to fabricate andthey require mounting. However, they provide unrivaled performance, withinductance values greater than 10 nH and quality factors greater than50.⁴⁰ Inductance values larger than one or two nH are physically largeand are typically placed off chip; these could benefit the most from aprinting technique. The pioneering work on inkjet-printed inductorsdemonstrates quality factors of ˜0.5.³⁸ More recently, meander inductorsand fully printed inductors have been shown with Q's approachingfive.^(36,37) A 25 nH inductor with a Q approaching nine was also shownin 2014.³⁸ All of these printed inductors utilize nanoparticle ink aswell as a sintering temperature greater than 150° C. In order to makerepeatable, quality RF components by inkjet, a robust metal ink withhigh conductivity is required.

The SOC ink developed here presents improved performance overnanoparticle ink and can provide high value inductors with qualityfactors approaching 15. A depiction of the dimensions of the inductorsas well as an image of the printed inductor is shown in FIGS. 8A and 8Brespectively.

Spiral inductors can be designed with Ansoft High Frequency StructureSimulator software. Both a one and a half turn and a two and a half turninductor can be fabricated. The devices can be measured with a networkanalyzer into the GHz regime, and the measured S-parameters from theanalyzer can be converted to Y-parameters.⁴¹ The return path and padsare de-embedded using a standard open short method to reduce parasiticeffects.⁴¹ After de-embedding, the inductance and quality factor arecalculated using equations (1) and (2).

$L = \frac{{im}( \frac{4}{Y_{11} + Y_{22} - Y_{12} - Y_{21}} )}{2\;\pi\; f}$$Q = {- ( \frac{{im}( {Y_{11} + Y_{22} - Y_{12} - Y_{21}} )}{{re}( {Y_{11} + Y_{22} - Y_{12} - Y_{21}} )} )}$

The dimensions of the inductors along with the measured parameters ofinductance, quality factors, and self-resonant frequencies arehighlighted in Table I.

TABLE 3 MEASURED INDUCTORS Dimensions Outer Inner Measured DiameterDiameter Gap Width L QF SRF Turn (mm) (mm) (μm) (μm) (nH) (max) (GHz)1.5 3.7 2.0 200 350 10.5 15 4 2.5 5.6 3.0 200 350 35.5 11 1.5 L =inductance, QF = quality factor, SRF = self-resonant frequency

The electromagnetic simulations show a match to the measured inductancevalues in FIGS. 9A-D, which demonstrate inductance and quality factorversus frequency for printed inductors of 1.5 (FIGS. 9A and 9Crespectively) and 2.5 turn(s) (FIGS. 9B and 9D respectively) supportedon PEN substrate. Two inductors were fabricated of each size validatingthe repeatability of the process. The measured inductors show qualityfactors above ten, which is can be considered state of the art forprinted inductors. This can be a step forward in making high qualitycomponents with a robust printing process.

This example presents a detailed study of an embodiment of the presentdisclosure in the form of a novel type of SOC ink; namely,silver-ethylamine-ethanolamine-formate-complex based robust ink. SOC inkmay have potential as a low cost alternative to nanoparticle basedsynthesis. It can provide high conductivities even at low temperatures˜150° C. It can be particle free and can be shown to have stable jettingfor more than 5 months. With appropriate additives the stablecomplexation may not be disturbed and excellent adhesion to a widevariety of substrates can be achieved. To demonstrate the capability ofthe ink, RF inductors have been realized which can be sensitive to theconductivity, thickness, and roughness of the printed metal. Ten to 35nH inkjet-printed spiral inductors on flexible plastic can exhibitmaximum quality factors greater than ten and self-resonant frequenciesabove 1.5 GHz. These are initial SOC inkjet-printed inductors and candemonstrate improved performance over nanoparticle based devices even ata lower temperature. This robust ink formulation can shows potential forsuitable high quality RF component fabrication as well as printedelectronics in general.

Materials and Methods

Chemicals:

Silver acetate (CH₃COOAg, ReagentPlus®, 99%), ethylamine (NH₂CH₂CH₃, 2Min methanol, ACS reagent), ethanolamine (NH₂CH₂CH₂OH, ACS reagent,≥99.0%), formic acid (HCOOH, reagent grade, ≥95.0%), and2-hydroxyethylcellulose (2-HEC, MW=90,000) were used as they werereceived, without further purification.

Ink-Formulation:

In an illustrative experiment, a 2M ethylamine solution in methanol,which was called as “Complexing Solution #1” was put in a vial. 10 mL ofethanolamine and 10 mL of deionized (DI) water (1:1 ratio) was mixed inanother a vial. Formic acid (η=1.78 mPa s, γ=37.67 mN/m, T_(b)=100.8°C.) can then be added to the solution in a drop-wise manner to adjustthe solution to pH 10.5. The resulting solution was called “ComplexingSolution #2”. In another vial, 1 g of silver acetate was vortex mixedwith 2 mL of complexing solution #1, 1.5 mL of complexing solution #2,and 0.5 mL of 2% 2-hydroxyethylcellulose (2% 2-HEC in water:methanol) atroom-temperature for 30 seconds, resulting in a light black coloredsolution. This finding demonstrates that 2-HEC not only acts asviscofier, it also acts as an additive for adhesion of the ink to thesubstrate. The as-obtained solution can then kept for twelve hours toallow any particles to settle out, yielding a clear supernatant, whichcan be decanted and filtered through a 200 nm syringe filter. This clearand transparent solution that contains approximately ˜17 wt % silver,served as the silver-ethylamine-ethanolamine-formate complex based SOCink.

Inkjet-Printing of SOC Ink:

The as-formulated SOC ink can be inkjet-printed on various substratesusing a variety of printers (such as a Dimatix printer) and/or printingprocesses, for example a drop-on-demand piezoelectric ink-jet nozzle(manufactured by Dimatix) with a diameter of 21 and 9 μm and drop volumeof 10 and 1 pL per print nozzle. The uniform and continuous ejection ofdroplets can be achieved by adjusting various wave-forms while applyinga firing voltage of 19-21 V at a 5 kHz printer velocity. In the presentexample, to quantify the number of drops for jetting stability test,five jets were chosen and their drop velocities of 5000 drops/s wereadjusted, which can jetted continuously for 120 seconds. Subsequently,the total jetted drops were weighed and they correspond to the dropmass. Then, total drop mass was divided by number of drops, whichprovided the average drop mass in nano-grams. The ink droplets weredispensed with a spacing of 20 μm and several fine line patterns andelectrodes (5 mm length and 0.25 mm width) were printed.

Fabrication and Measurement of Printed Inductors:

The inductors can be fabricated on PET substrate (t=125 μm) using fivelayers of AOC ink at 20 um drop spacing with a 10 pL Dimatix DMP 2831inkjet printer. In the example, the ink was heated at 150° C. for 30minutes in an oven after each layer was printed. A universal lasersystem PLS6.75 was utilized to cut via holes and make a connection withthe underside of the inductors. Three layers of ink were printed toconnect the vias and DuPont 5000 conductive paste and fill the laserdrilled via holes. The inductors were measured in a two portconfiguration using 500 μm pitch Z-probes and a cascade probe station.An Agilent E8361A network analyzer was used to characterize the devices.

Characterization:

The structural properties can be examined using scanning electronmicroscopy (FEI NovaNano FEG-SEM 630). Measurements of the thickness anduniformity of printed features on substrates can be performed using asurface profiler (Veeco Dektak 150), 3D interferometry (Zygo, Newview7300), and cross-sectional SEM images. The film thickness on flexiblePEN substrate can be performed by milling through FIB tool (Quanta 3DFEG). Crystallinity of the silver film can be examined by X-raydiffraction (Bruker D8 Advance) in the range of 20-80° C. at 40 kV. TheUV-Vis absorption spectrum of the ink can be obtained using a UV-Visspectrophotometer (Cary 100 UV-Vis-NIR) with a standard 1 cm liquidcuvette, and with a background calibration run using deionized water.Surface tension and Rheology of the inks can be measured using a KRUSSTensiometer and Rheometer (Bohlin Gemini 2). Thermogravimetric analysiswas performed using a TG 209 F1 analyzer (Netzsch), which was equippedwith TGA-IR (Tensor 27, Bruker), at a temperature range of 25-300° C.;it had a heating rate of 10° C./min in air flow. For isothermalthermogravimetric analysis, heating rate of 5° C./min was provided toreach the isothermal temperature. Differential scanning calorimetry(DSC) was observed by a STA 449 F1 (Netzsch) analyzer in nitrogen flow.Electrical resistances of silver electrodes were measured with afour-point probe method (Keithley 4200-SCS).

References

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A 32 nm SoC Platform    Technology with 2nd Generation High-k/Metal Gate Transistors    Optimized for Ultra Low Power, High Performance, and High Density    Product Applications, Electron Devices Meeting (IEDM), IEEE    International 2009, 1-4.-   (40) High Q-multilayer Chip Inductor for High Frequency    Applications,” Taiyo Yuden Corp., Product Data Sheet, October 2011.-   (41) Frickey, D. A. Conversions Between S, Z, Y, H, ABCD, and T    Parameters which are Valid for Complex Source and Load Impedances.    IEEE Trans. Microwave Theory Technology 1994, 42, 205-211.

Example 2

Fully inkjet-printed 3D objects with integrated metal provide excitingpossibilities for on-demand fabrication of radio frequency electronicssuch as inductors, capacitors and filters. To date, there have beenseveral reports of printed radio frequency components metallized via theuse of plating solutions, sputtering, and low-conductivity pastes. Thesemetallization techniques require rather complex fabrication and do notprovide an easily integrated or versatile process.

This example utilizes a novel silver ink cured with a low-cost infraredlamp at only 80° C. and achieves a high conductivity of 1×107 S/m. Byinkjet printing the infrared-cured silver together with a commercial 3Dinkjet ultraviolet-cured acrylic dielectric, a multilayer process isdemonstrated. By using a smoothing technique, both the conductive inkand dielectric provide surface roughness values of less than 500 nm. Aradio frequency inductor and capacitor exhibit state-of-the-art qualityfactors of 8 and 20, respectively, and match well with electromagneticsimulations. These components are implemented in a lumped element radiofrequency filter with an impressive insertion loss of 0.8 dB at 1 GHz,proving the utility of the process for sensitive radio frequencyapplications.

One of the major advancements in inkjet printing has been the use ofUV-cured acrylic materials. These liquid inks immediately solidify uponexposure to a low-cost UV lamp, and, like acrylic paints, they can bemade with vibrant colors. This concept has been extended beyond graphicarts by using hundreds of inkjet nozzles to form fully printed 3Dacrylic parts in minutes. Although multi-jet technology is still in itsinfancy, commercial multi-jet printers are now available.1 A majoradvantage of the 3D multi-jet process over other 3D printing methods,such as stereolithography, selective laser sintering, or fuseddeposition modeling, is that multiple materials can be easily depositedtogether, just as an inkjet head routinely prints with cyan, magenta,yellow and black. Thus far, multi-jet printing has been restricted tothe colorful UV-cured acrylics and wax/gel support materials. Fullyprinting objects with an integrated high-conductivity metal providesexciting possibilities for additive and on-demand fabrication of radiofrequency electronics such as inductors, capacitors and filters.

To date, there have been several reports of printed objectsincorporating metal, focused on RF applications, by using platingsolutions, aerosol, sputtering, and low-conductivity pastes.^(2,3,4)These metallization techniques require rather complex fabrication and donot provide an easily integrated or versatile process. Previous reportshave also put the spotlight on other issues with 3D printing techniquesfor electronics fabrication, such as micrometer surface roughness andlow conductivity of the metal.⁵ A recent report by Wu et al. shows anovel concept of 3D printing, together with syringe injection of asilver paste at 70° C., to create 3D inductors and capacitors; however,the conductive paste achieves a low conductivity of 2.8×105 S/m,approximately 200 times less than that of bulk silver.² In our previouswork, silver nanoparticles were utilized to metallize a 3D printedantenna, but the particles required selective laser sintering of theparticles to avoid damaging the acrylic material and achieved aconductivity of only 1×106 S/m.⁶ A major challenge of fully printingelectronics is that the high temperature required for the metal isincompatible with the printed dielectric.

Most of the previous work on inkjet-printed Radio Frequency (RF)passives is focused on 2D inkjet printing of metal on a standardsubstrate. Redinger et al. reported some of the first work on 2D printedcapacitors and inductors in 2004, utilizing nanoparticles but achievingrather low quality factors (Q's) of ˜0.5.7 Since then, there have beenmaterial and printing advancements enabling 2D printed inductors andcapacitors with high-frequency Q's below^(10,8,9,10) To our knowledge,the combination of these fully printed components to design a GHz lumpedelement filter has never been demonstrated. Distributed 2D RF filtersare generally simpler to print than lumped element filters. Previousdistributed filter results have shown inadequate performance, with theinsertion loss ranging from 3.6 to 10 dB.^(11,12,13,14,15) One of thebest reports has shown an insertion loss of approximately 0.5 dB at itscenter frequency (2 GHz), but it utilized inkjet printing along withelectroless plating to increase the conductivity and thickness of themetal.¹⁶

This example provides a process beyond 2D inkjet printing of theconductor on a standard support substrate; the metal is truly integratedinto the printed dielectric to build quality multilayer RF capacitorsand inductors with crossover interconnects. An advancement is the lowprocessing temperature (80° C.) of the novel Silver-Organo-Complex (SOC)ink, which overcomes the challenge of temperature processingcompatibility between the printed conductor and dielectric. The SOC inkis cured with a low-cost IR lamp in only 5 minutes while providingstate-of-the-art conductivity of 1×107 S/m, which is necessary forconductivity-sensitive RF filter applications.

Materials and Methods

Ultraviolet-Cured Dielectric Ink

Stratasys UV-cured ink is sold under the name Vero™ and comes indifferent colors and hardnesses. From the material safety data sheet ofVeroWhite™, it is composed mostly of acrylic monomers (<30%), isobornylacrylate (<25%), and various other components, including acrylateoligomers and urethane acrylates.^(17,18) Less than 1% titanium dioxideis used for the white color. The photoinitiator is Diphenyl-2,4,6trimethylbenzoyl oxide (<2%), which produces a free radical upon UVexposure, initiating the polymer reaction of the acrylic monomers andoligomers to form a hardened acrylic part. The acrylic monomers areliquid at room temperature but too viscous for jetting at 125 cp; seeFIG. 10A.

Although the UV dielectric ink is tailored for the Stratasys Objetproduct line of 3D inkjet printers, it was more convenient to print witha Dimatix 2831 printer. It is worth noting that by adjusting theviscosity and surface tension of the solution complex ink-chemistry,this type of ink can be used for various deposition techniques (e.g.,spin-coating, direct ink writing, fine nozzle printing, airbrushspraying, screen printing, and roll-to-roll processing methods). TheDimatix printer allows control over nearly all print settings. By usinga jetting temperature of 60° C., the viscosity of the dielectric inkdrops to 20 cp, as shown in FIG. 10A, allowing for excellent jettingfrom the Dimatix 10-pL print head. The ink does not show any change inviscosity over the three different shear rate measurements shown in FIG.10A. The average drop in mass of the UV-cured ink jetted at 60° C. and a9-m/s velocity is 9.6 ng, measured by ejecting five million drops andweighing the total. Throughout this work, the UV-cured ink is printedwith two layers at 30 μm, with drop spacing forming 11-μm-thick layers.For curing, it is exposed to 7500 mJ/cm² of 365-nm-wavelength lightafter printing.

After UV curing, thermogravimetric analysis was completed to understandthe thermal limits of the material; see FIG. 10B. The TGA shows thatthere is negligible mass loss up to 150° C.; however, the materialspecification sheet reports the glass transition for the materialapproximately 47-53° C., and it was found experimentally that there isextreme warping of the material over 80° C.¹⁹ Therefore, it may benecessary to have a conductor that can be processed at temperaturesunder 80° C.

To design radio frequency components, it is important to know thedielectric properties. From the parallel plate measurements (FIG. 10C,10D), the VeroWhite™ material has a dielectric constant of ˜3.0 and adissipation factor of ˜0.02 up to 1 GHz. The dissipation factor of thematerial is rather high and can cause attenuation of the RF signal;however, FR-4 also has a dissipation factor of 0.02 and is the go-tomaterial for low-cost RF applications.²⁰ Overall, this material isadequate for many RF designs but does have appreciable dielectric loss,and it has limitations in terms of temperature range (<45° C.) thatshould be respected.

Infrared-Cured Silver-Organo-Complex Ink

The SOC ink utilized herein has been developed in-house to overcome theissues with conventional metal nanoparticle ink. While silvernanoparticle ink has been widely investigated and is availablecommercially, it has a complex synthesis protocol, high cost, and highsintering temperature (>150° C.), and exhibits particle aggregation,nozzle clogging, a poor shelf life, and jetting instability. Through theuse of smaller nanoparticles (˜10 nm) and a more robust ink formulation,commercial silver ink performance has improved in recent years. However,in the long term, it is difficult to avoid particle aggregation andprecipitation in a nanoparticle system.

Organometallic inks are another approach to printing conductivepatterns. They contain dissolved precursors of metallic elements bondedwith organics (i.e., silver acetate, silver oxalate and copperhexanoate).^(21,22,23) In general, the organometallic bond is broken,and the organic molecule evaporates away, leaving a metal film behind.In the past, organometallics have been less successful than theirnanoparticle counterparts. One issue has been bubble formation,resulting in rough porous thin films as noted by Walker et al.²⁴

An in-house SOC ink is utilized in this work, and it is capable ofproducing smooth and dense films; it is stable and transparent, asdescried herein.²⁵ The SOC ink produces films with an impressive 1×107S/m, 20% of the bulk conductivity at only 80° C. Along with the highconductivity at low temperatures, the ink exhibits strong adhesion,long-term stability (>5 months in a print head), and robust jettingperformance. Briefly, the ink is based on a silver salt, anorgano-complex of a first complexing agent that can be an alkylamine anda second complexing agent that can be an aminoalcohol, and a short chaincarboxylic acid. In this particular example, the ink is based on asilver acetate complex with ethylamine, ethanolamine, water, methanoland 2-hydroxyethyl cellulose (HEC) (Mw˜90,000), where the HEC is anadditive that acts as both viscosity modifier and adhesion promoter. Thewater and methanol serve as solvents.

The fluid parameters and operating points of both the SOC ink and theVeroWhite™ dielectric ink are given in Table 4. The Reynolds, Weber,Ohnesorge, and capillary number are provided since inks are often mappedby these parameters to fit in a specific jetting space. To determine thefluid properties the SOC ink is measured at 25° C. with a jettingvelocity of 10 m/s. VeroWhite™ dielectric ink is measured at 60° C. witha jetting velocity at 9 m/s velocity. Both inks utilize a Dimatix 10-pLDMC cartridge with a 21-μm-diameter nozzle. Although the SOC ink has alower viscosity than the dielectric ink at 5.9 compared to 20 cp, bothinks have good jetting stability and fit within the jetting spaceoutlined by Derby et al.²⁶

TABLE 4 Surface Drop Ink Viscosity T. Density Mass Type (cp) Dyne/cm(g/cc) (ng) (Oh) (Re) (We) (Ca) SOC Ink 5.9 30.7 1.17 7.0 0.21 41.6 80.01.9 VeroWhite ™ 20.0 30.2 1.1 9.6 0.75 10.4 62 6.0 Dielectric InkSurface T. = Surface Tension, Oh = Ohnesorge, Re = Reynolds, We = Weber,Ca = Capillary.

The conductivity of the SOC ink has been tested as a function of layerthickness, as shown in FIG. 11A. The conductivity of the ink approaches2×107 S/m at 150° C. and 1×107 S/m at 80° C. with increased overprints.Note that the 150° C. heating was achieved on a glass substrate sincethe acrylic material would deform at temperatures above 80° C. Alow-cost 250-watt IR lamp is used to cure the ink by putting thesubstrate under the light for five minutes after each printed layer. Themaximum measured temperature of the substrate is 80° C. This method wascapable of achieving a high conductivity of 1×107 S/m by approximately 6overprints.

From the cross-section of Scanning Electron Microscopy (SEM) images(FIGS. 12A-12H), there are clear voids in the printed film that aresubsequently filled in by the overprints. More overprints result in adense film with higher conductivity.

Via 8 overprints and IR curing cycles, the film is fairly dense andapproximately 5-μm-thick, as seen in FIG. 11B.

Adhesion was a concern for the ink, and it was found experimentally thatthe addition of 0.02 wt. % 2-HEC solved the issue while increasingviscosity for superior jetting. Adhesion to glass, PET, and the 3Dprinted materials was tested with scotch tape without any removal of thesilver film. The ink is stable over the long term, as tested with aDimatix 10-pL cartridge over five months with no observable reduction inthe overall drop mass. Additionally, the printed films showed nosignificant difference in conductivity after 10 months aging inenvironmental conditions.

Fabrication Process

A depiction of the complete inkjet process is shown in FIG. 13, Steps(i)-(vii). Two different printers were utilized, the Objet 3D multijetprinter and Dimatix 2831 research printer, for convenience. The multijetprinter allows quick processing of the UV material, while the Dimatixprinter allows for more control over all of the print parameters andcuring. It is easy to envision a single inkjet system or production linecapable of performing all printing and curing.

First, the UV cure material is printed with the Objet 3D printer,allowing for complex and thick shapes to be printed (Step (i), FIG. 13).After 3D printing, the substrate has several micrometers of surfaceroughness, as shown in FIG. 15A. This roughness is substantialconsidering that the printed metal thickness itself is less than amicrometer per layer. Surface roughness is especially detrimental in RFcomponents since it causes attenuation of the signal. The roughnessissue is tackled by jetting an additional “smoothing” layer ofdielectric ink (FIG. 15B) with the Dimatix 2831 inkjet printer and 10-pLhead (Step (ii), FIG. 13). After deposition, the ink is allowed tospread before UV curing, and eventually, it smoothens the surface to 0.4μm of RMS roughness. The SOC ink can then be printed on this smoothlayer and cured with IR heating (Step (iii), FIG. 13). Next, in step(iv), the dielectric ink is printed with the Dimatix, and the dielectricink covers the silver ink and is again cured with a UV lamp. Finally, inStep (v), another layer of SOC ink can be printed, creating a multilayerprocess where the top and bottom layers are connected with crossovers. Across-section depiction of the process is shown in FIG. 13, Step (vi).Note that the silver and dielectric printing (iv-v) could be repeated tocreate several layers for more complex electronics designs. An image ofa fully printed part is shown in FIG. 13, Step (vii).

One difficulty to overcome during the fabrication was the wetting of thedielectric VeroWhite™ ink on the silver layer. The dielectric inkspreads excessively on the solid silver layer underneath. To optimizethe wetting condition, a perfluorodecanethiol (PFDT) treatment was used.This treatment has been demonstrated by Tseng et al. to increase thesurface hydrophobicity of printed electrodes.²⁷ The parts are dipped ina bath of 0.28 mL PFDT with 100 mL of IPA, then rinsed in IPA and driedwith nitrogen. The change can be seen in the contact angle measurementof the dielectric, as is shown in FIG. 14. Without treatment, the inkspreads uncontrollably on the surface (note that all images are taken 5seconds upon impact). After 10 minutes of surface treatment, the contactangle was stable at 65° C., and high definition patterns were possiblewith the dielectric ink on top of the silver. This allows for thedielectric and silver to be printed in a multilayer fashion capable offabricating RF passives.

Experimental

Silver-Organo-Complex Ink Formulation

In an illustrative experiment, a 2 M ethylamine (NH2CH2CH3, ACS reagent)solution in methanol, which was called “Complexing Solution #1,” was putin a vial. 10 mL of ethanolamine (NH2CH2CH2OH, ACS reagent, ≥99.0%) and10 mL of deionized (DI) water (1:1 ratio) were mixed in another vial.Formic acid (HCOOH, reagent grade, ≥95.0%) was then added to thesolution in a drop-wise manner to adjust the solution to a pH of 10.5.The resulting solution was called “Complexing Solution #2.” In anothervial, 1 g of silver acetate (CH3COOAg, ReagentPlus®, 99%) was vortexmixed with 2 mL of complexing solution #1, 1.5 mL of complexing solution#2, and 0.5 mL of 2% 2-hydroxyethylcellulose (2% 2-HEC in water:methanolMW=90,000) at room-temperature for 30 seconds, resulting in a lightblack-colored solution. 2-HEC not only acts as a viscosifier, it alsoacts as an additive for adhesion of the ink to the substrate. Theas-obtained solution was then kept for twelve hours to allow anyparticles to settle out, yielding a clear supernatant, which wasdecanted and filtered through a 200-nm syringe filter. This clear andtransparent solution, containing approximately ˜17 wt % silver, servedas the silver-ethylamine-ethanolamine-formate complex-based SOC ink.²⁵

Characterization of the Capacitor, Inductor and Filter

Capacitors were measured with an Agilent 4980A LCR meter. The leakagecurrent was measured with a Keithley 4200-SCS. High-frequencymeasurements of the passive devices were taken in a two-portconfiguration using 500-μm-pitch Z-probes and a cascade probe stationwith an Agilent E8361A network analyzer. The structural properties wereexamined using scanning electron microscopy (FEI NovaNano FEG-SEM 630).The thickness and uniformity of printed features on substrates weremeasured using a surface profiler (Veeco Dektak 150) and 3Dinterferometry (Zygo, Newview 7300). The surface tension and viscosityof the inks were measured using a KRUSS DSA100 and Brookfield Rheometer(DV3T). Thermogravimetric analysis was performed using a TG 209 F1analyzer (Netzsch), with a heating rate of 10° C./min in air flow.

Results

Low-Frequency Capacitor Characterization

To evaluate the process, Metal Insulator Metal (MIM) capacitors werefirst printed with the SOC ink for electrodes and the dielectric inkusing the process previously described. Capacitors allow forcharacterization of the leakage current, dielectric, behavior andquality factor at low frequency. The printed capacitors have excellentleakage current values of approximately 1×10-10 A/cm2 at 0.08 MV/cm,equivalent to 100 V across the 11-μm-thick capacitor. The capacitorswere also tested against frequency and temperature; see FIG. 16A, 16B.While the dielectric constant in FIG. 16A is relatively flat with afrequency (˜3) up to 45° C., the material shows considerablelow-frequency dispersion at elevated measurement temperatures. Thistemperature issue can also be seen in the decrease in the quality factorshown in FIG. 16B. After cooling to room temperature, the dielectricproperties return to the 25° C. case.

This is a known behavior in acrylic materials, caused from dielectricrelaxation at the glass transition temperature, (˜50° C.). A thoroughinvestigation of the dielectric relaxation in thin acrylic sheets hasbeen studied by Wubbenhost et al., who described this phenomenon.²⁸ Acomplete characterization of the dielectric relaxation with temperaturefor this material is out of the scope of the present disclosure. Theimportant point is that the dielectric properties are sensitive totemperature and should be operated below the glass transition. Humidityimpacts the capacitors, providing a ˜10% normalized capacitance increaseaccompanied by a quality factor reduction when tested from 25% relativehumidity to 85% relative humidity. The dielectric has also been testedagainst voltage bias and shows ideal behavior with negligible change incapacitance value or quality factor. The major changes in both physicaland electrical dielectric properties occur at elevated temperature.However, there is no issue as long as the material is fabricated below80° C. to avoid excessive warping and operated below 45° C. to avoiddielectric changes at the glass transition temperature.

High Frequency Characterization of the Capacitor, Inductor and Filter

The capacitor, inductor and filter were all measured at high frequencieswith a vector network analyzer in a two-port configuration.Electromagnetic models of the devices were created using Ansoft HighFrequency Structure Simulator (HFSS) software with the appropriateconductivity, thickness and dielectric properties to compare withmeasurements. From the network analyzer, the measured S-parameters arede-embedded with an open-short method and are converted to Y-parametersat each frequency point f, which is a standard procedure.^(29,30) Thefollowing equations are used to convert to capacitance C, inductance L,and quality factor Q.

$\begin{matrix}{C = \frac{1}{{{im}( \frac{4}{Y_{11} + Y_{22} - Y_{12} - Y_{21}} )}2\;\pi\; f}} & (1) \\{L = \frac{{im}( \frac{4}{Y_{11} + Y_{22} - Y_{12} - Y_{21}} )}{2\;\pi\; f}} & (2) \\{Q = {- ( \frac{{im}( {Y_{11} + Y_{22} - Y_{12} - Y_{21}} )}{{re}( {Y_{11} + Y_{22} - Y_{12} - Y_{21}} )} )}} & (3) \\\; & (4)\end{matrix}$

FIGS. 17A, 7B show the quality factor and the capacitance value as afunction of frequency, respectively. The capacitor is 2 pF and has aself-resonant frequency of 6.5 GHz. The quality factor of the capacitorstarts out at 25 and drops down to zero at self-resonance as expected.The quality factor results are also consistent with the measured devicesat lower frequency and 25° C., as shown in FIG. 14A. It should be notedthat previous printed dielectrics have had difficulty achieving suchhigh quality factors in the high MHz and GHz regime, typically reportingQ's lower than 10, largely due to the loss tangent of the dielectricsused.^(8,9)

An inductor has also been tested, as shown in FIGS. 17C, 17D. This 1.5turn inductor has an outer diameter of 4 mm with a 600-μm-thick spiral,has a self-resonance at 4 GHz and is approximately 8 nH at a frequencyof 1 GHz. The quality factor in simulation (FIG. 17D) is slightly higherthan the measured results (FIG. 17C). This is likely due to there beinggreater resistance from the printed silver ink than simulated; theinductors are extremely sensitive to the conductivity and thickness ofthe printed ink. These inductors have been printed with five layers ofSOC ink and show a peak quality factor of ˜8. The quality factors forboth the inductors and capacitors are considered state-of-the-art amonginkjet-printed passives, even with the low 80° C. processingtemperature.^(8,9)

The capacitor and inductor were implemented in a classic Butterworth lowpass filter with a cutoff frequency of 2.0 GHz.31 The Butterworth filterprovides a maximally flat passband, and the low pass filter was designedin a full-wave EM simulation in Ansoft HFSS to finalize the layout. FIG.18A shows a microscopy image of the fabricated filter. There is an insetdepicting the corresponding placement of the capacitor and inductor forclarity. The capacitor area is further visualized by the cross-sectionalSEM image in FIG. 18B. From the cut, the printed silver thickness atboth layers and the 11-μm-thick dielectric spacing of the capacitor areclear. The measured frequency response of the filter in FIGS. 18C, 18Dmatches well with the HFSS simulation with a 3-dB cutoff at 2 GHz. Thereis signal rejection near 10 dB at 3 GHz and better than 20 dB at 4 GHz.The filter has no ripple in the passband, as expected, and an insertionloss of 0.8 dB at 1 GHz from the zoomed-in response of FIG. 18D. The lowinsertion loss is excellent for a first ever fully inkjet-printed lumpedelement filter, especially considering the temperature constraints of80° C. The performance is state of the art, even compared to previous 2Ddistributed printed filters where nanoparticles are printed on astandard substrate, reporting insertion losses ranging from 3.6 to 10dB.^(11,12,13,14,15)

Discussion

Inkjet printing is transitioning from solely a graphic arts medium intoa useful fabrication tool. The ability to deposit multiple materials andthe scalability of inkjet systems with hundreds of nozzles make itpossible to realize large and complex parts. A process is presentedherein in which inkjet-printed UV-cured polymer and silver ink areintegrated together. A major challenge is integrating a metal with thelow-temperature UV-cured plastic material. The novel SOC ink presentedherein has been deployed, developed in-house, and provides aconductivity of 1×107 S/m at 80° C. to combine the materialseffectively. The combination of quick (5-minute) IR curing of the silverand rapid UV curing of the polymer in an ambient environment makes thisan attractive method for fabrication. The capacitor and inductor exhibitstate-of-the-art quality factors of ˜20 and 8, respectively, in theradio frequency regime and compare well with electromagnetic simulationmodels. By implementing these components, a low pass filter has beenfabricated with an insertion loss of 0.8 dB at 1 GHz.

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Ratios, concentrations, amounts, and other numerical data may beexpressed in a range format. It is to be understood that such a rangeformat is used for convenience and brevity, and should be interpreted ina flexible manner to include not only the numerical values explicitlyrecited as the limits of the range, but also to include all theindividual numerical values or sub-ranges encompassed within that rangeas if each numerical value and sub-range is explicitly recited. Toillustrate, a concentration range of “about 0.1% to about 5%” should beinterpreted to include not only the explicitly recited concentration ofabout 0.1% to about 5%, but also include individual concentrations(e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%,3.3%, and 4.4%) within the indicated range. In an embodiment, the term“about” can include traditional rounding according to significant figureof the numerical value. In addition, the phrase “about ‘x’ to ‘y’”includes “about ‘x’ to about ‘y’”.

It should be emphasized that the above-described embodiments are merelyexamples of possible implementations. Many variations and modificationsmay be made to the above-described embodiments without departing fromthe principles of the present disclosure. All such modifications andvariations are intended to be included herein within the scope of thisdisclosure and protected by the following claims.

Therefore, the following is claimed:
 1. An ink composition for making asilver structure, the ink composition comprising asilver-organo-complex, a solvent, an anion of acetic acid and an anionof formic acid; wherein the silver-organo-complex comprises a silvercation complexed with a first complexing agent and a second complexingagent; wherein the first complexing agent is an alkyl amine and thesecond complexing agent is an alkanolamine.
 2. The ink composition ofclaim 1, wherein the alkyl amine is selected from the group consistingof methylamine, ethylamine, propylamine, butylamine, and amylamine. 3.The ink composition of claim 1, wherein the alkanolamine is selectedfrom the group consisting of methanolamine, ethanolamine, propanolamine,and butanolamine.
 4. The ink composition of claim 1, wherein the inkcomposition has a pH of 9-14.
 5. The ink composition of claim 1, whereinsaid ink composition further comprises an additive selected from thegroup consisting of 2-hydroxyethylcellulose (2-HEC), 2,3-butanediol,glycerol, ethylene glycol, and combinations thereof.
 6. The inkcomposition of claim 5, wherein the ink composition comprises 2-HEChaving a molecular weight of 90,000.
 7. The ink composition of claim 1,wherein said solvent is selected from the group consisting of water,short chain alcohols having an alkyl chain of 1-3 carbon atoms, and acombination thereof.
 8. The ink composition of claim 1, wherein the inkcomposition has a viscosity of about 4.95 mPa·s to about 5.97 mPa·s. 9.The ink composition of claim 1, wherein the ink composition has asurface tension of about 30.7 mN/m to about 33.08 mN/m.
 10. The inkcomposition of claim 1, wherein the ink composition has a sinteringtemperature of about 80° C. to about 150° C.
 11. The ink composition ofclaim 1, wherein the alkyl amine is ethylamine and the alkanolamine isethanolamine.
 12. A method of forming a conductive silver structure,comprising: depositing an ink composition according to claim 1 onto asurface using a nozzle of an inkjet printing head; and reducing said inkcomposition deposited on said surface.
 13. The method of claim 12,wherein the conductive silver structure is a Radio-Frequency (RF)electronic device.
 14. The method of claim 13, wherein said nozzle is a1 pL to a 10 pL piezoelectric nozzle.
 15. The method of claim 14,wherein said surface is selected from the group consisting of polyimide(PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN),glass, and 3D printed substrates.
 16. The method of claim 15, whereinsaid reducing is sintering at a temperature of about 80° C. to about150° C.
 17. The method of claim 16, further comprising: depositing asecond layer of the ink composition on the sintered ink composition; andsintering the second layer of the deposited ink composition.
 18. Themethod of claim 16, wherein ink composition further comprises anadditive selected from the group consisting of 2-HEC having a molecularweight of 90,000 and 2,3-butanediol.
 19. A method of making an inkcomposition, comprising: combining a first complexing solution, a secondcomplexing solution, and a silver salt to form a silver-organo-complex,wherein the first complexing solution comprises an alkyl amine, and thesecond complexing solution comprises an alkanolamine and a carboxylicacid, and the silver-organo-complex comprises a silver cation complexedwith the alkyl amine and the alkanolamine; and filtering the inkcomposition to produce a clear and transparent solution.
 20. The methodof claim 19, further comprising preparing the second complexing solutionby adding the carboxylic acid to the alkanolamine to adjust the pH to9-10.5.